CN112899887A - Temperature-adjusting anti-fouling fiber membrane and temperature-adjusting anti-fouling breathable double-layer fiber membrane based on same - Google Patents
Temperature-adjusting anti-fouling fiber membrane and temperature-adjusting anti-fouling breathable double-layer fiber membrane based on same Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4374—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece using different kinds of webs, e.g. by layering webs
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Abstract
The invention discloses a temperature-regulating antifouling fiber membrane and a temperature-regulating antifouling breathable double-layer fiber membrane based on the same, wherein the temperature-regulating antifouling fiber membrane is formed by temperature-regulating antifouling fibers of a core-shell structure (the shell is a hollow Cu-containing shell)7S4PVDF and n-eicosane serving as cores of the nano particles) are added, and the temperature-regulating anti-fouling fiber membrane and the sweat-releasing breathable PAN fiber membrane are compounded to obtain the temperature-regulating anti-fouling breathable double-layer fiber membrane. The fiber membrane obtained by the invention has excellent temperature regulation, stain resistance and air permeability, and the process method is simple and easy to operate and is easy for industrial production.
Description
Technical Field
The invention belongs to the field of multifunctional fiber membrane preparation, and particularly relates to a temperature-regulating antifouling fiber membrane and a temperature-regulating antifouling breathable double-layer fiber membrane based on the same.
Background
With the continuous development of science and technology and peopleWith the increasing living standard, the development of textiles towards intellectualization and multi-functionalization is also beginning, and the temperature control function of the textiles is receiving much attention. The photo-thermal conversion material can quickly convert solar energy into heat energy under the sunlight, and long-term heat supply under a low-temperature environment is realized, so that a functional layer containing a proper photo-thermal conversion material is compounded in the textile, and the temperature regulation function of the textile can be realized. Copper-based metal sulfide (Cu)2-xS) the micro-nano material is an important non-stoichiometric P-type semiconductor material, has a strong absorption effect on near infrared light due to a Local Surface Plasmon Resonance (LSPR), can improve the heat utilization rate of solar energy, and has a wide application prospect in a photo-thermal conversion device.
According to research and application of the photothermal conversion material, although continuous heat energy supply can be realized by the photothermal conversion material under sunlight, the photothermal conversion material also dissipates heat very quickly, and the storage and control of heat cannot be realized. The composite fast-response high-energy-storage phase change medium stores/releases heat energy by utilizing an absorption/release conversion mode carried out when the phase change material undergoes phase change, or can solve the problem. The n-eicosane is a solid-liquid phase change material, has the melting point of 36.52 ℃, the crystallization point of 26.06 ℃, is close to the temperature of a human body, has large phase change latent heat, does not need supercooling or precipitation, has stable chemical and thermal properties, small density and low price, and has the advantages of high heat storage density, small temperature change in the heat charging and discharging process and the like.
In addition to the development of new functions, the improvement of basic functions such as antifouling and air permeability is also receiving much attention. The anti-fouling and air-permeable performance of the fabric can meet the requirements of people on resisting stains, rainwater and the like in the outdoor environment, and sweat steam emitted by a human body can be diffused or transmitted to the outside through the fabric, so that condensation is not accumulated between the body surface and the fabric, the human body does not feel stuffy, and the wearing comfort is kept. However, the main existing technology for manufacturing the anti-fouling breathable film has the problems of complex processing technology, high technical and equipment requirements, difficulty in regulating and controlling the pore structure and the like, so that the application and development of the anti-fouling breathable fabric are limited. The electrospinning technique is a method of solidifying into nanofibers by solvent evaporation or melt cooling. Various types of nanofibers such as organic nanofibers, inorganic nanofibers, organic and inorganic composite nanofibers and the like are successfully prepared by the electrostatic spinning technology, and random nanofiber membranes, orderly arranged nanofiber bundles and single nanofibers can be obtained by designing different fiber receiving devices. And the nanofiber prepared by electrostatic spinning has higher specific surface area and adsorption property, is beneficial to the transfer of water vapor/sweat, and the film has the characteristics of high isotropy, high porosity among fibers, uniform distribution and the like. The technology can adjust process parameters according to the requirements of fabric products to obtain films with different structures and thicknesses, and has great application potential in the field of preparation and processing of high-performance anti-fouling breathable films. Meanwhile, by regulating and controlling the technological parameters of electrostatic spinning, the leakage problem of the phase-change material can be effectively prevented, and the energy storage and temperature control performance of the nanofiber membrane is ensured.
In conclusion, the advantages of the existing anti-fouling breathable fiber membrane are combined with the characteristics of the phase-change energy storage material and the photothermal conversion material, so that the multifunctional temperature-regulating anti-fouling breathable nanofiber membrane with large specific surface area and good flexibility is formed, and the multifunctional temperature-regulating anti-fouling breathable nanofiber membrane has wide application prospects. Therefore, a method for realizing the combination of the phase-change material and the electrostatic spinning nanofiber membrane is necessary, and the influence of the photothermal conversion material on the performance of the nanofiber membrane is avoided.
Disclosure of Invention
The invention aims to provide a temperature-regulating anti-fouling fiber membrane with good anti-fouling performance, high photo-thermal conversion efficiency and excellent intelligent temperature control performance and a temperature-regulating anti-fouling breathable double-layer fiber membrane based on the temperature-regulating anti-fouling fiber membrane so as to realize intellectualization and multifunctionality of textiles.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly discloses a temperature-regulating antifouling fiber membrane, which is characterized in that: the temperature-regulating anti-fouling fiber membrane is formed by temperature-regulating anti-fouling fibers with a core-shell structure; the temperature-adjusting anti-fouling fiber contains hollow Cu7S4The PVDF solution of the nano particles is a shell material solution, and n-eicosane dissolved into liquid is a core material solution, and the nano particles are prepared by coaxial melting electrospinning.
Further, the hollow Cu7S4The mass ratio of the nanoparticles to the PVDF is 0.1-0.2: 1.
The preparation method of the temperature-regulating anti-fouling fiber membrane comprises the following steps:
step 1, adding hollow Cu into PVDF dispersion liquid taking DMF as solvent7S4Magnetically stirring the nano particles until the nano particles are uniformly dispersed, and then standing and defoaming to obtain a shell material solution;
and 3, respectively adding the shell material solution and the core material solution into an injector, connecting the injector with a coaxial needle head, placing the injector in electrostatic spinning equipment, and performing electrostatic spinning in an induction charging mode to obtain the temperature-regulating anti-fouling fiber membrane.
Furthermore, in the shell material solution in the step 1, the mass concentration of PVDF is 10 wt% -13 wt%.
Further, in the step 3, the temperature of the phase-change material n-eicosane in the injector and the needle is higher than the melting temperature thereof, so that the phase-change material is prevented from crystallizing in the injector and the needle to cause blockage due to too low ambient temperature.
Further, in step 3, the electrostatic spinning conditions are as follows: the spinning voltage is 14-16 kV, the feeding speeds of the shell material injection pump and the core material injection pump are 20-25 mu L/min and 3-5 mu L/min respectively, and the distance between the needle head and the receiving device is 13-15 cm.
The invention also discloses a temperature-regulating antifouling breathable double-layer fiber film, which is formed by compounding the temperature-regulating antifouling fiber film and a sweat-releasing breathable fiber film; the sweat-discharging breathable fiber film is obtained by carrying out uniaxial electrostatic spinning on a DMF (dimethyl formamide) solution of PAN.
The preparation method of the temperature-regulating antifouling breathable double-layer fiber membrane comprises the following steps: firstly, preparing a temperature-regulating anti-fouling fiber membrane according to the preparation method; and then, before the temperature-regulating anti-fouling fiber membrane is dried, carrying out uniaxial electrostatic spinning on the DMF solution of PAN on the surface of the temperature-regulating anti-fouling fiber membrane to form a PAN fiber membrane, namely obtaining a double-layer fiber membrane.
Further, the mass concentration of PAN in the DMF solution of PAN is 10-13 wt%; the spinning voltage of the single-shaft electrostatic spinning is 18-20 kV, the feeding speed of the injection pump is 18-20 mu L/min, and the distance between the needle head and the receiving device is 13-15 cm.
The temperature-regulating antifouling fiber membrane or the temperature-regulating antifouling breathable double-layer fiber membrane can be applied as a textile functional layer.
The invention has the beneficial effects that:
1. the temperature-regulating antifouling fiber membrane combines a phase-change material n-eicosane with an energy-storing and temperature-regulating function and Cu with a near-infrared and visible light absorption function7S4The photo-thermal conversion material increases the absorption and conversion efficiency of light energy, and enables the fiber film to have the characteristic of rapid solar-thermal energy conversion/storage. Meanwhile, the temperature-regulating anti-fouling fiber membrane has a large contact angle and good anti-fouling performance.
2. Cu added in the temperature-regulating anti-fouling fiber membrane7S4The dosage of the nano particles can be adjusted according to the practical application environment, so that the adjustment of personal heat protection can be realized, and more Cu can be added7S4The nano particles improve the conversion of solar energy and heat energy, so that the fiber membrane can reach higher temperature under sunlight and is used in the field of high-temperature heating.
3. The invention can change the diameter of the fiber and the porosity of the film by adjusting the technological parameters of electrostatic spinning, including the injection speed, the voltage and the electrospinning time of the internal and external spinning solutions, so that the diameter and the porosity of the film can be controllably adjusted according to the requirements of temperature adjustment and comfort, and the invention can be produced in batch in practical application.
4. The double-layer fiber membrane prepared by the invention has the functions of energy storage and temperature regulation, and also has very good stain resistance and air permeability.
5. The warm anti-fouling fiber membrane prepared by the invention can be applied to the field of comfortable functional fibers, and the specific infrared absorption function of the warm anti-fouling fiber membrane is expected to make a breakthrough in the field of infrared shielding.
6. The process method is simple and easy to operate, the preparation conditions are controllable, the industrial production is easy, the obtained fiber membrane can realize the long-term spontaneous heating function of the fabric under the irradiation of sunlight, and the phase-change temperature control technology can effectively reduce daily temperature fluctuation and is beneficial to maintaining the comfortable feeling of a human body.
Drawings
FIG. 1 shows PVDF nanofiber membranes and PVDF/Cu films obtained in examples 1 to 47S4Graph comparing the illumination time-temperature curve of the nanofiber membrane with that of a common Black Cloth (Black Cloth);
FIG. 2 shows PVDF nanofiber membranes obtained in example 1 and PVDF/Cu membranes obtained in example 47S4Nanofiber Membrane and PCM @ PVDF nanofiber Membrane obtained in example 5 and PCM @ PVDF/Cu obtained in example 67S4A comparison graph of the illumination time-temperature curve of the nanofiber membrane;
FIG. 3 shows the PCM @ PVDF/Cu obtained in example 67S4A graph comparing the heat stability of washing;
FIG. 4 is an SEM image of the temperature-regulating, stain-resistant, breathable two-layer fibrous membrane obtained in example 7;
FIG. 5 is a schematic representation of the sweat absorption and fast drying performance of the temperature regulated soil resistant breathable bilayer fibrous membrane obtained in example 7.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. The following disclosure is merely exemplary and illustrative of the inventive concept, and those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Hollow Cu used in the following examples7S4The preparation steps of the nano-particles are as follows:
0.1996g of copper acetate and 0.2g of PVP (K-30) are dissolved in 30mL of deionized water, and after uniform magnetic stirring at room temperature, 10mL of solution with the concentration of 1mol is dripped into the solutionThe mixture was stirred for 30min with/L aqueous NaOH solution, and a blue precipitate appeared in the solution. Then 10mL of ascorbic acid aqueous solution with the concentration of 0.3mol/L is rapidly added, the mixture is magnetically stirred for 30min under the condition of heating to 55 ℃, and brick red Cu is obtained2And (4) O product. Finally, 20mL of Na with a concentration of 0.15mol/L was directly added to the mixed solution2S·9H2O, stirring is continued for 1h at 55 ℃. After the reaction is finished, naturally cooling the mixed solution to room temperature, centrifugally separating, cleaning for 3-4 times by using ultrapure water and absolute ethyl alcohol, and drying in vacuum to obtain the hollow Cu7S4A nanoparticle powder.
The PVDF used in the examples described below has a relative molecular mass of 1000,000 g.mol-1The selected solvent DMF has certain volatility and can well dissolve PVDF and Cu7S4。
Preparation of temperature-regulating anti-fouling fiber membrane
Example 1
Step 1, weighing 0.88g of PVDF powder at room temperature, adding the PVDF powder into 8g of DMF, heating and stirring for 2h at 60 ℃, standing and defoaming for 10min to obtain a DMF solution of PVDF with the mass concentration of 10 wt%.
And 2, injecting the PVDF DMF solution obtained in the step 1 into a 10mL injector as a spinning precursor solution, connecting the injector with a single-shaft needle, placing the injector into electrostatic spinning equipment, and performing electrostatic spinning by adopting an induction charging mode (namely, direct-current high voltage is directly connected to a spinning needle, and an aluminum foil receiving device is grounded) to prepare the hydrophobic PVDF nanofiber membrane. The conditions of electrostatic spinning are as follows: the spinning voltage was 14kV, the solution injection pump feed rate was 25. mu.L/min, the distance between the needle and the receiving device was 15cm, and the drum speed was 500. + -. 10 rpm.
Through tests, the PVDF nanofiber membrane obtained in the embodiment has a contact angle of 128.4 degrees and a water vapor transmission rate of 11.3kg · m-2·d-1(12.0 kg. m for pure cotton fabric)-2·d-1) The surface temperature of the film rises by about 4.5 ℃ under the simulated illumination condition, and the fastest heating rate is 4.4 ℃/min.
Example 2
Step 1, weighing 0.88g PVDF powder at room temperatureAdding the mixed solution into 8g of DMF, heating and stirring the mixed solution for 2 hours at the temperature of 60 ℃, standing and defoaming the mixed solution for 10 minutes to obtain a DMF solution of PVDF with the mass concentration of 10 wt%. Then 0.088g of photothermal conversion material Cu was added7S4Slowly adding the powder into the clear solution, stirring at room temperature for 12h to uniformly disperse the powder in the solution, standing and defoaming to obtain Cu7S4And the mass ratio of the solution to PVDF is 0.1: 1.
After testing, the PVDF/Cu obtained in this example7S4(1:0.1) the contact angle of the nanofiber membrane was 137.2 °. The composite film has good photo-thermal conversion performance, the surface temperature of the film is raised by about 23.5 ℃ after the irradiation of simulated sunlight, and the fastest heating rate reaches 20.0 ℃/min.
Example 3
Step 1, weighing 0.88g of PVDF powder at room temperature, adding the PVDF powder into 8g of DMF, heating and stirring for 2h at 60 ℃, standing and defoaming for 10min to obtain a DMF solution of PVDF with the mass concentration of 10 wt%. Then 0.132g of photothermal conversion material Cu was added7S4Slowly adding the powder into the clear solution, stirring at room temperature for 12h to uniformly disperse the powder in the solution, standing and defoaming to obtain Cu7S4And the mass ratio of the solution to PVDF is 0.15: 1.
After testing, the PVDF/Cu obtained in this example7S4(1:0.15) the contact angle of the nanofiber membrane was 140.0 °. The composite film has good photo-thermal conversion performance, the surface temperature of the film is raised by about 23.9 ℃ after the irradiation of simulated sunlight, and the fastest heating rate reaches 21.0 ℃/min.
Example 4
Step 1, weighing 0.88g of PVDF powder at room temperature, adding the PVDF powder into 8g of DMF, heating and stirring for 2h at 60 ℃, standing and defoaming for 10min to obtain a DMF solution of PVDF with the mass concentration of 10 wt%. Then 0.176g of photothermal conversion material Cu7S4Slowly adding the powder into the clear solution, stirring at room temperature for 12h to uniformly disperse the powder in the solution, standing and defoaming to obtain Cu7S4And the mass ratio of the solution to PVDF is 0.2: 1.
After testing, the PVDF/Cu obtained in this example7S4(1:0.2) the contact angle of the nanofiber membrane was 145.8 °. The composite film has good photo-thermal conversion performance, the surface temperature of the film is raised by about 25.3 ℃ after the irradiation of simulated sunlight, and the fastest heating rate reaches 22.5 ℃/min.
Example 5
Step 1, weighing 0.88g of PVDF powder at room temperature, adding the PVDF powder into 8g of DMF, heating and stirring for 2h at 60 ℃, standing and defoaming for 10min to obtain a DMF solution of PVDF with the mass concentration of 10 wt% as a shell solution.
And 2, adding n-eicosane (PCM) into a beaker, and heating to 60 ℃ to dissolve the n-eicosane into liquid to obtain a core material solution.
And 3, respectively adding the shell material solution and the core material solution into an injector, connecting the injector with a coaxial needle, placing the injector in electrostatic spinning equipment, and performing electrostatic spinning in an induction charging mode to obtain the hydrophobic PCM @ PVDF nanofiber membrane with the core-shell structure. The conditions of electrostatic spinning are as follows: the spinning voltage is 14kV, the feeding speeds of the shell material injection pump and the core material injection pump are respectively 25 mu L/min and 5 mu L/min, the distance between the needle head and the receiving device is 15cm, and the rotating speed of the roller is 500 +/-10 rpm.
The contact angle of the PCM @ PVDF nanofiber film obtained in this example was tested to be 133.4 °. The latent heat of the fiber film is 97.88J/g by DSC, and the coating rate of the phase-change material is calculated to reach 44.7 percent.
Example 6
Step 1, weighing 0.88g of PVDF powder at room temperature, adding the PVDF powder into 8g of DMF, heating and stirring for 2h at 60 ℃, standing and defoaming for 10min to obtain a DMF solution of PVDF with the mass concentration of 10 wt%. Then 0.176g of photothermal conversion material Cu7S4Slowly adding the powder into the clear solution, stirring at room temperature for 12h to uniformly disperse the powder in the solution, standing and defoaming to obtain Cu7S4And (3) taking the uniform solution as a shell material solution, wherein the mass ratio of the uniform solution to the PVDF is 0.2: 1.
And 2, adding n-eicosane (PCM) into a beaker, and heating to 60 ℃ to dissolve the n-eicosane into liquid to obtain a core material solution.
After testing, the PCM @ PVDF/Cu obtained in this example7S4The nanofiber membrane had a contact angle of 151.8 ° and a water vapor transmission rate of 9.2kg · m-2·d-1(12.0 kg. m for pure cotton fabric)-2·d-1). The composite film has good photo-thermal conversion performance, and the surface temperature of the film is increased by about 25.3 ℃ after the irradiation of simulated sunlight. And after the light source is turned off, the surface temperature of the fabric is maintained within the comfortable temperature range of the human body.
FIG. 1 shows PVDF nanofiber membranes and PVDF/Cu films obtained in examples 1 to 47S4Graph comparing the illumination time-temperature curves of nanofiber membrane and common Black Cloth (Black Cloth). It can be seen from the figure that with Cu7S4The mass increases and the maximum temperature reached at the surface of the fiber membrane gradually increases, significantly above the maximum temperature of the surface of the pure PVDF fiber membrane (about 24 ℃). Explanation, hollow Cu7S4The nano particles can improve PVDF/Cu7S4Heat storage efficiency of nanofiber membranes. In addition, PVDF/Cu7S4The heating rate of the nanofiber membrane can reach 22.5 ℃/min at the highest. Meanwhile, the common black cloth with the same thickness is selected for comparison, the black cloth also has a certain degree of solar energy-heat energy conversion, but the highest temperature can only reach about 38 ℃, the fastest heating rate is 16.2 ℃/min, and is obviously lower than PVDF/Cu7S4The rate of temperature increase of the nanofibers (22.5 ℃/min). The above results show that PVDF/Cu7S4The nanofiber membrane has a fast solar-thermal conversion efficiency.
FIG. 2 shows PVDF nanofiber membranes obtained in example 1 and PVDF/Cu membranes obtained in example 47S4Nanofiber Membrane and PCM @ PVDF nanofiber Membrane obtained in example 5 and PCM @ PVDF/Cu obtained in example 67S4Graph comparing the illumination time-temperature curve of the nanofiber membrane. It can be seen from the figure that the phase change material releases heat in the low temperature crystallization process, the maximum surface temperature of the PCM @ PVDF nanofiber membrane is higher than that of the pure PVDF nanofiber, but the total amount of the phase change material coated in the PCM @ PVDF nanofiber is very smallThe maximum temperature is only about 29.5 ℃. Meanwhile, under the condition of simulating sunlight, PCM @ PVDF/Cu7S4The nanofiber membrane can rapidly realize solar energy-thermal energy conversion. The phase-change material absorbs heat by melting, and the PVDF/Cu is restrained7S4The continuous temperature rise of the nanofiber membrane, so the curve has a short-term "plateau" phenomenon. When the simulated solar light source is turned off, the temperature is reduced, the phase-change material is crystallized to release the stored heat energy, and the PCM @ PVDF/Cu is caused7S4The cooling rate of the fiber membrane is obviously lower than that of PVDF/Cu7S4Fibrous membranes, which ultimately maintain them at a temperature at which the human body is comfortable. Further proves that the phase-change material temperature control technology can effectively reduce daily temperature fluctuation and help the skin to keep a comfortable level.
FIG. 3 shows the PCM @ PVDF/Cu obtained in example 67S4The washing thermal stability of the nanofiber membrane is compared with that of the nanofiber membrane, and the test method is to use PCM @ PVDF/Cu7S4And ultrasonically soaking the nanofiber membrane in water for 0h, 24h, 72h and 120h respectively. After each soaking washing and drying cycle, the photothermal properties were measured under infrared lamp irradiation. It can be seen from the figure that after 24h of soaking wash, the PCM @ PVDF/Cu7S4The temperature of the nanofiber membrane increased by about 37.86 ℃ under the irradiation of an infrared lamp compared to PCM @ PVDF/Cu without washing treatment7S4The nanofiber membrane temperature was essentially the same (about 38.18 ℃). After 72h and 120h soaking cycles, the temperature rose by about 35.5 ℃, which was slightly lower than after the first wash, probably due to some Cu on the fiber surface under the effect of the megasonic waves7S4Loss of nanoparticles, mostly Cu overall7S4Nanoparticles and PCM @ PVDF/Cu7S4The fibers are tightly bound and exhibit good photo-thermal stability.
Preparation of temperature-regulating antifouling breathable double-layer fiber membrane
Example 7
The two-layer fiber membrane of this example was a temperature conditioned stain resistant PCM @ PVDF/Cu prepared from example 67S4The fiber film is compounded with the sweat-discharging breathable fiber film; row boardThe sweat-permeable fibrous membrane is obtained by uniaxial electrospinning a DMF solution of PAN. The method comprises the following specific steps:
step 1, PCM @ PVDF/Cu7S4Preparation of fibrous membranes
The same as in example 6.
0.55g of hydrophilic polyacrylonitrile (PAN, Mw 150,000) was dissolved in 5g of DMF, heated and stirred at 60 ℃ for 2 hours, and left to stand for deaeration for 10min to obtain a PAN solution having a concentration of 10 wt%.
The prepared PAN solution was injected into a 10mL syringe, which was attached to a single-axis needle and placed in an electrospinning apparatus. PCM @ PVDF/Cu prepared in step 17S4Before the fiber film is dried, the fiber film is taken as a base material, and the collection is continued on the surface of the fiber film, so that the double-layer film has good adhesion. The conditions of electrostatic spinning are as follows: the spinning voltage is set to be 18kV, the sample injection rate is 20 mu L/min, the receiving distance is 15cm, and the rotating speed of the roller is 500 +/-10 rpm. At the end of spinning, a temperature-regulating, dirt-resistant and breathable double-layer fiber membrane with a thickness of about 129 μm is obtained, wherein the intelligent temperature control layer (namely PCM @ PVDF/Cu)7S4Fiber film) thickness of about 71 + -1.0 μm, and perspiration-permeable layer thickness of about 58 + -1.0 μm.
FIG. 4 is an SEM image of the temperature-regulating, stain-resistant, and air-permeable bi-layer fiber membrane obtained in this example, from which it can be seen that PAN fibers and shell layers with uniform diameter distribution are doped with Cu7S4PCM @ PVDF/Cu of7S4The fiber and the prepared nano fiber have high specific surface area and porosity.
Fig. 5 is a schematic diagram of the sweat-absorbing and quick-drying performance of the temperature-regulating, anti-fouling and breathable double-layer fiber membrane obtained in the embodiment, and it can be seen from the diagram that the PAN nanofiber membrane in contact with the skin layer has good hydrophilicity, and can rapidly absorb sweat and evaporate the sweat, so that the surface of the skin is dry and comfortable.
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A temperature-regulating anti-fouling fiber membrane is characterized in that: the temperature-regulating anti-fouling fiber membrane is formed by temperature-regulating anti-fouling fibers with a core-shell structure; the temperature-adjusting anti-fouling fiber contains hollow Cu7S4The PVDF solution of the nano particles is a shell material solution, and n-eicosane dissolved into liquid is a core material solution, and the nano particles are prepared by coaxial melting electrospinning.
2. The temperature regulating anti-fouling fibrous membrane of claim 1, characterized in that: the hollow Cu7S4The mass ratio of the nanoparticles to the PVDF is 0.1-0.2: 1.
3. A process for the preparation of a temperature regulating antifouling fibrous membrane according to claim 1 or 2, characterized in that:
step 1, adding hollow Cu into PVDF dispersion liquid taking DMF as solvent7S4Magnetically stirring the nano particles until the nano particles are uniformly dispersed, and then standing and defoaming to obtain a shell material solution;
step 2, adding n-eicosane into a beaker, and heating at 50-60 ℃ to dissolve the n-eicosane into liquid to obtain a core material solution;
and 3, respectively adding the shell material solution and the core material solution into an injector, connecting the injector with a coaxial needle head, placing the injector in electrostatic spinning equipment, and performing electrostatic spinning in an induction charging mode to obtain the temperature-regulating anti-fouling fiber membrane.
4. The production method according to claim 3, characterized in that: in the shell solution in the step 1, the mass concentration of PVDF is 10-13 wt%.
5. The production method according to claim 3, characterized in that: in step 3, the temperature of the phase change material n-eicosane in the injector and the needle is higher than the melting temperature thereof.
6. The production method according to claim 3, characterized in that: in step 3, the electrostatic spinning conditions are as follows: the spinning voltage is 14-16 kV, the feeding speeds of the shell material injection pump and the core material injection pump are 20-25 mu L/min and 3-5 mu L/min respectively, and the distance between the needle head and the receiving device is 13-15 cm.
7. The utility model provides a double-deck fibrous membrane that the dirt-resistant is ventilative adjusts the temperature which characterized in that: the double-layer fiber film is formed by compounding the temperature-adjusting anti-fouling fiber film and the perspiration-discharging breathable fiber film according to claim 1; the sweat-discharging breathable fiber film is obtained by carrying out uniaxial electrostatic spinning on a DMF (dimethyl formamide) solution of PAN.
8. A method for preparing the temperature-regulating antifouling breathable double-layer fiber membrane as claimed in claim 7, wherein the method comprises the following steps: firstly, preparing a temperature-adjusting anti-fouling fiber membrane according to the preparation method of any one of claims 3-6; and then, before the temperature-regulating anti-fouling fiber membrane is dried, carrying out uniaxial electrostatic spinning on the DMF solution of PAN on the surface of the temperature-regulating anti-fouling fiber membrane to form a PAN fiber membrane, namely obtaining a double-layer fiber membrane.
9. The method of claim 8, wherein: the mass concentration of PAN in the DMF solution of PAN is 10-13 wt%; the spinning voltage of the single-shaft electrostatic spinning is 18-20 kV, the feeding speed of the injection pump is 18-20 mu L/min, and the distance between the needle head and the receiving device is 13-15 cm.
10. Use of a thermoregulating antifouling fibrous membrane according to claim 1 or of a thermoregulating antifouling breathable bilayer fibrous membrane according to claim 7 as a functional layer of a textile.
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